Conversion of fluid reactants



Jan. 14', 19.47. G. GRHOLDv 2,414,373

Y CONVERSION OF FLUID REACTANTAS Filed'ApIil 12, 1944 ggf, zg/33232223157 529%@ zzy 6705 aseaas P/"oc/a cfs Patented Jan. 14, 1947 UNITED STATES PATENT QFFICE CNVERSIUN OF, FLUID REAGTANTS Clarence G. Gerhold, Chicago, Ill." assigner to Universal Oil Products Company, Chicago,'l1l.,

a corporation ofDelaware Application April 12, 1944, Serial No. 530,641

(Cl. 19E-52) 5 Claims. 1

The invention is` directed to an improved method and meansfor eiecting the conversion of fluid reactants in the presence of a mass of subdivided solid contact material. or catalyst Whchaccumulates deleterious products of the reaction andis regeneratedby removal ofthe contaminants.

'Ihe system provided is` of the general type in` whichfthe` conversion` reaction and regeneration are accomplished simultaneously in separate con-- fined. reactionand regenerating Zones through which the catalystror` contact material is continuously circulated. Itis furthercharacterized in that a. relatively compactbed of the solidparticles is` maintained inthe reaction zongand in the regenerating zone. Thefluidreactants to be converted and .resulting iluid conversion products are passedupwardly through the bed inthe re-4 action zonewhile the solid particles of catalyst l The features ofthe invention willbeiound. aclvantageous as applied to a,.widevarietyof .reacftions involving the sequential l contact. oi subdivided l solid material with.. different fluids. Therefore, in its. broader aspectsthe. invention is not otherwise limited 'with respect to the Vparticular class of operation conducted. Also, in its broad aspects the process may employsolidcontactmaterial vwhich is eitherrelatively-inert in directing or promotingthe reaction erhasl a cata? lytic influence thereon or is a` reagent which enters into'the reaction. However, the invention is more particularlydirected to the catalytic conversion of fluidhydrocarbons by such reactions asI cracking, reforming, dehydrogenation, aromatization cr dehydrocyclization and the like. Operating conditions of temperature, pressure, contact timeY andthe like, as well as solidcatalysts suitable fonpromoting the desired reaction, arev scriptiorr4 will, therefore; `be directed :principally` tothis type tof "operation and the applicability of thelfeatures. ofthe invention to other opera?.

tions.. of the general class above mentioned will.

be readily apparent to those familiarlwith the art.

ticles of catalyst.. or ,contact lmaterial `flow downwardly by gravity inseries through the 1several, contacting Zones counter-current` tothe. fluidswith which they are contacted therein. A further object isto providesuch. anoperationin which` the `kinetic energy. of the .outgoinglfluid .from ene of .the contacting zones is.` utilizedto advantage4 by employing the fluidas atransporting-medium for returning solid` particlesL from the. lowerzone` fjthe series to a relatively highlpointfin thesystem. from fwhich they will .flowlby gravity .back

through .the contacting zones.

As` applied to the Vcatalytic cracking of` hydrocarbon-oil, the aforementioned; objectsof the.,

invention maybe achieved, for example, 'hy` providing a .disengaging vessel .and catalyst` hopper in which the. circulating catalyst particles are separated from the..transporting. fluid and.in which. a. relatively compact mass ofthe catalyst particles is accumulated, providing a reaction ves-.U

sel communicating with said hopper and disposed therebeneath' to whichthe-hydrocarbon reactantsto be converted are supplied'. and therein contacted with. arelativelycompact bed of the cata.- lyst to effect their conversion, providing a regenerating vessel communicating with and disposed,

beneath .the reactor` and to which Vvair or other oxidizing `gasis supplied` and passedin contact with `the .'bed of the catalyst in this Zone 'to burn..

combustibles therefrom, removing. gaseous prod.- ucts of the regeneratingistepfrom the bed in the regenerating zone and from the latter, separatelyremovingregenerated catalyst particlesfrom .tlief lower portion of thebed in the regenerating.zone,.

suspending: the same in. a streamof .transportinggas comprising at least a portion of saidgase ous products l of regeneration. and directing` the.`

suspensionupwardlyby thegas-lift action of the transporting fluid intok theA aforesaid disen The invention also contemplates the use oftstripping vessels Aatap-V gaging vessel fand, hopper.

-propriatelocations in the catalyst circuit above describedfor substantially purging occluded and adsorbed volatile i hydrocarbons from the catalyst passing from the reactor .to `the regeneratorand for substantially purgingthe. occluded and ad.-

scrb'ed oxidizinggas and. combustiongases, fromV the stream. .of Catalyst particles being transferred yfrom the regenerator to the reactor.

The aforementioned and other features of the invention will be described in more detail with reference to the accompanying diagrammatic drawing.

The drawing is an elevational view of one speciiic form of apparatus in which the improved process provided by the invention may be conducted. l l

Referring to the drawing, the apparatus here illustrated comprises a disengaging vessel and catalyst hopper I wherein transporting gas and suspended catalyst particles, supplied thereto as will be later described, are substantially separated and wherein a relatively compact mass of the catalyst particles is accumulated. The approximate upper extremity of the catalyst mass or bed in vessel I is indicated by the broken line 2. An uninterrupted relatively dense or compact column of catalyst particles extends downwardly from the mass or bed in vessel I through the stripping column 3, conduit 4, the reaction vessel 5, conduit @stripping column 1, conduit 8, the regenerating vessel 9 and conduit IIl into the gaslift transfer line I I wherein solid particles which have passed downwardly through the sequence of lines and vessels above mentioned are sus pended in a stream of transporting gas and returned therein to the disengaging vessel and hopper I to complete the main catalyst circuit through the system.

In loperating the process for the catalytic crackn ing of hydrocarbon oil, the latter is supplied to the lower. portion of reactor through line I2 and valve I3,` preferably in essentially vaporous state, and the oil vapors are directed upwardly through a suitable perforate distributing member I4 into the relatively compact bed of downwardly moving catalyst particles I5 supported by member I4. Suitable cracking conditions of temperature, pressure and space velocity are maintained within the reaction zone to effect the desired cracking of the hydrocarbon reactants as they pass upwardly through bed` I 5. The term space velocityf as. here used may be defined as pounds of hydrocarbon reactants supplied to the reaction zone per4 hour, per pound of catalyst present in the reaction zone.

The approximate upper extremity of bed I5 in the reactor is indicated by the broken line I6 and the vaporous and gaseous hydrocarbon conversion products are dischargedfrom the bed intovthe space lprovided between the upper extremity of the bed and the upper end of the reaction vessel. These products are discharged from the reactor through line Il and valve I8, preferably to fractionating and recovery equipment of any desired conventional form which does not constitute a novel part of the system and is, therefore, not illustrated. In case any substantial quantity of catalyst nes remain entrained in the vapor-gas stream discharged from the reactor through line I'I they may be separated Y therefrom and recovered by passing the stream through suitable equipment, not illustrated, such as one or more centrifugal or cyclone separators, an electrical precipitator, a scrubber or the like. This also applies to the recovery of catalyst nes from any of the other outgoing vapor and/or gas streams discharged from the several vessels.

As previously indicated, the perforate member I4 in the reactor serves as a distributing grid for substantially uniformly distributing the incomingr hydrocarbon reactants over the horizontal cross-sectional area of the catalyst bed in the reactor and serves also as a screen having Sumciently small openings to prevent the solid particles from passing therethrough. The catalyst particles pass downwardly over member I4 into conduit 6 through which they now into another relatively dense bed I9 maintained within stripping column l. Here the catalyst particles from the reactor, which have accumulated deleterious contaminantswhich must lbe burned` therefrom in the'regenerator to restore the desired activity to the catalyst, are substantially stripped of occluded and adsorbed volatile hydrocarbons in order to prevent the passage of these more valuable fractions into the regenerator where they would be burned with the heavy contaminants. To accomplish this Vsuitable stripping gas, such as steam, carbon dioxide, nitrogen or other relatively inert gas, is supplied to the lower portion of the stripping column through line 2f! and valve 2I and is directed upwardly through the perforate distributing member 22, similar in form and function t0 that of member I4 in the reactor, into andvupwardlythrough bed I9 to strip out volatile hydrocarbons from the bed, Y

The approximate upper extremity of the bed I3 in stripping column v'I is. indicated by .the

broken line 23 and the stripping gasand stripped y out volatiles are discharged from the space provided between the upper extremity of bed I9 and the upper end of stripping column 'I through line 24 and valve 25. This outgoing stream may conveniently be supplied, when desired, to the same fractionating and recovery equipmentV above mentioned to which the vapor gas stream from the reactor issupplied so that the stripped-out the catalyst by passing oxidizing gas upwardly into bed 26 in contact with and countercurrent to the downwardly moving catalyst particles comprising the bed. The regenerating gas employed, which may comprise, for example, air or air diluted with relatively inert or non-combustible gas is supplied to the lower portion of theregenerator through line 2'I and valve 28, entering the vessel beneath the perforate member and screen 30, and Y is passed upwardly through the latter into bed 26. Member 3 is also similar in form and function to member I4 in the reactor.

The approximate upper extremity of the catalyst bed in the regenerator is indicated by the broken line 3| and the gaseous products of combustion, resulting from regeneration of the catalyst, are discharged from the space provided in the regenerator between its upper end and the upper extremity of bed 26 through line 32. That portion, if any, of the gases thus discharged from d the regenerator, which is not required for trans- 30 porting the regenerated catalyst back to vessel I, as willbe later described, may be discharged from the system through valve 33 in line 32 to suitable heat recovery equipment or the like, not illustrated, which may be provided in this line for the recovery of readily available heat energy from th hot combustion gases. i

The catalyst which has undergone regeneration in regenerator 9 is directed from the lower portion of bed 2B downwardly through conduit i 5 IIII and the adjustable orice or flow control valve 34 .provided `adjacent -the lower .end of this foonduit` into .the gas-lift transfer `line I-I. regenerated catalyst particles meet A.andare sus- .pended in a `stream of .transporting gas which, inthe case illustrated, mayfcomprisealloraregulated `portion .of -the gaseous products of regenerationpreviously discharged from the regenerator. The gaseous products .of Vregeneration are supplied to transfer line II :from line 432 .through line35 and yalve v35. The Vtransportinggas serves to .increase the Velocity and reduce the catalyst particle concentration Lor Ydensity of the stream passing through transfer line II, so that the-hydrostati'c pressure in line .-II =at the point Where the .catalyst particles enter thesame fis Ymaterially less than :the hydrostatic pressure -on the upstream side :of `valve 34 in the more dense catalyst column passing through the vessels .I, 3"57, -1 9 .and the communicatinglines 4, y6, 8 and '|0. Thus, the catalyst particles are transported iupwardly through .line I=I by the gas-.lift laction of theoutgoing regenerating gas and the required kineticenergyoi the .transporting :gasmay be obtained .by maintaining a `higher gas `pressure vat the outlet endof the regenerator and in lines 3.2 and l35 .than that maintained :in the disengaging vessel .-I to which the catalyst is transported. In any case, the pressure `of the transporting `gas entering transfer -line I I Vis sufficiently `greater than :the ygas pressure in vessel I to overcome the pressure=drop through line IAI and carry the catalyst particles therethrough, 'but is somewhat less than -the hydrostatic ,pressure zon `.the upstream side of valve 34.

Vessel -I may, when desired, be open at its upperend-to the atmosphere so that the pressure in this zone is substantiallyatmospheric, or la slight superatmospheric pressure `may be "employed in this zone'and thegases which havebeen disengaged from the .catalyst particles therein are discharged from .the vessel through line 3'I, controlled by valve 38. This outgoingigasstream will comprise .transporting `gas utilized kin transfer line .II and stripping gas utilized, as will be later described, :in stripping column 3. Separation of all or substantially allof the catalyst particles from thegasesin vessel .I iseiectedin *the case illustrated, .by gravitation of :the solid particles, 'the `velocity .of v'the :gases being reduced 'in the enlarged .upper section of vessel I .to such an extent that they "will not overcome the 4force of gravity on the .solid particles and 'the latter will settle from the gases.

The 'separated regenerated catalyst accumulatedwithin the hopper-like bottom section vof vessel I mayretalin occluded and adsorbed transporting gas and stripping column 3 is provided, in the case illustrated. as azone Ain whicha'll or a substantial vportion of these occluded and `adsorbed 4gases vare stripped or purged from `the catalyst to prevent their introduction into the reactor. To accomplish this, Ystripping gas of the v.nature `previously "mentioned "in connection with lthe operation lof stripper I is supplied to the 'lower portion of stripping column 3 through line 39 and valve 4d, entering this zone `beneath the perforate distributing grid and screen 4I which is `similarin form and function to member I4 in Athe reactor. The stripping gas ,flows upwardly through member .4I .and the .column of downwardly moving .catalystparticles in the stripping z one 'to displace other gases. Strippingfluid and stripped-.out gases .pass from the upper `extremity' 2 of the mass of catalyst .in hopperI to Here the `commi-ngle with the transporting gas 4from line I-I and to be discharged therewith through line` 31 and valve 38.

In case it `is desired to remove the .stripping `fluid andstripped-out gases from column 3 vseparate from the transporting fluid .supplied to vessel I, stripping column 3 may be .separate from vessel I with a standpipe from the latter extending downwardly to the `bed `in the stripping column in the `same `manner .as `conduit :16

extends into stripping column 1. Thus, stripping :tion of the `bed I5 in reactor 5 where they are again used to promote the cracking reaction, as previously described.

Provision is made, in the case here illustrated, for cooling `the catalyst being returned from the regenerator to the reactor in 'order to maintain the desired `average temperature inthe bed I5 in the reactor and so that a considerably higher vtemperature may Abe employed in the regenerator, as is usually desirable. To accomplish this a heat exchanger 43 `is interposed :in the gas-lift transfer line II and a suitable cooling medium, such as water, steam, Ihot oil, moltenfsalt or -the like, is circulated through the heat eX- changer in indirect Ycontact and heat transfer relation with the stream of .commingled catalyst particles vand transporting uid passing therethrough. The cooling 'fluid is supplied to heat exchanger 43 through line 44 `and isdischarged at an increased temperature through .line '45 'at a rate controlled Vby valve 46.

.It is, fof course, Apossible and within the scope of the invention to `interpose Va `heat exchanger or catalyst 4cooler similar :to 43 in conduit 4 .or in conduit l-I Il `or at any `other desired point 4in the path `of "flow of .fthe :catalyst passing 4from the regenerator back to ithe 'reactor or'to provide heat exchange `means within the regenerator. However, byiproriding equipment for -coolingthe catalyst in `the gas-.lift transfer line 'I I, it will also .serve .to .recover 'heat `:from the outgoing gaseous `products of regeneration. Also, when Aa catalyst `cooler 'is vprovided .in line Il, or in line III) `or "vessel LI, Acooled 'catalyst may 'be withdrawn f-rom vessel .fI and returned directly and in regulated 4Quantities to fthe -upper portion of bed 26 in .theregenerator iso as to prevent `the development Aof .an fexcessively high temperature in this zone Iwhich would lresult in `demage or permanent impairment to the activity of the catalyst. In the `case illustrated, provision is made for Withdrawing cooled :catalyst "fromwessel l and directingth'e same 'through conduit 4'! and the adjustable forice for ifl'ow control valve T48, `provi-died Tat the .lower en@` thereof, into conduit `8 `to commingle 4with and reduce tothe desired degree porting medium other .than v'gaseous products of'v regeneration may .be :employed `-in: transfer line III .in addition yto .or 'instead ofj'gases discharged from the fregenerator. .Provision i's'lmade 4in fthe case illustrated :for supplying .otherftransprtsubstantially non-oxidizing gas, such as combustion gases produced outside the regenerator and relatively low in free oxygen and vcarbon mon- CFI oxide content, or it may comprise oxidizing gas,

such as air, which may, when desired, be subsequently used toA support combustion in the regenerator. vIn the latter case (i. e., when air o1' other .oxidizing gas from an external source yis employed as the transporting fluid in line I I) it may be supplied, after being disengaged from .the 'catalyst in vessel I, to the lower portion of regenerator 9 by a suitable connecting-conduit, not illustrated.

:.ffIhe invention also contemplates omission of the catalystcooler- 43 or equipment serving a similar function and disposed, as previously mentioned, at another point in the system and/or to omit line 41 and valve 48 through which cooled catalyst may be returned directly to the regenerator. These features will be unnecessary when the endothermic conversion step conducted in reactor I and the exothermic regenerating oper ation conducted in regenerator 9 are substantially balanced thermally so that the combustibles deposited on the catalyst in the reactor and burned therefrom in the regenerator store in the regenerated catalyst returned to the reactor al1-or that portion of the endothermic heat of reaction which it is desired to impart to the reactants within the reactor.' However, use ofthe catalyst cooler, as well as provision for returning cooled regenerated catalyst directly to the regenerator, will lend greater flexibility to the process with respect to choice of charging stock and operating conditions.

' The preferred embodiment 'of the invention, illustrated and above described in'conjunction with the drawing, is particularly advantageous in securing a pressure balance Within the system to take advantage of gravity now of the catalyst from the disengaging zone and hopper through the-reactor, regenerator and interconnecting lines and stripping vessels while obtaining return of the catalyst through line II to the disengaging zone by the gas-lift action of outgoing products of regeneration. As an illustration, assuming that the reactants and fluid conversion products encounter a pressuredrop vof approximately live pounds in passing through the reactor and ap`` proximately the same pressure drop is-encoun tered by the oxidizing gas and resultingfcombustion gases in passing through the regenerator andv that a gas pressure of approximately five pounds gauge is employed in the disengaging zona-oxidizing gas may be supplied to the regenerator through line 2'I and valve 28 at an inlet pressure of approximately fifteen pounds gauge. This will give a pressure of approximately ten pounds gauge for the gaseous prod'-v uctsfofregeneration entering transfer line II. The reactants may be supplied to reactor 5 through line I2 and valve I3 at a gauge pressure of` approximately ten pounds and fluid con# version products will be discharged from the reactor through line I'I and valve I8 ata pressur of` approximately five pounds gauge.

Under the conditions above' given,'hydrostatic pressure on the relatively dense' stream or column ofcatalyst entering the reactor will be somewhat 1 greater thanthe gas pressure above bed I5 in the reactor :sothat the vaporous vand gaseous con-f version products will .not passv lupwardly 'throughconduit 4, but win he discharged through une 1i rand valve I 8. Also, the' hydrostatic pressure on the relatively dense streamlor column of-catalyst entering the regenerator is somewhat greater than the gas pressure in the regenerator above bed 2B so that the gaseous products of regeneration will' not flow upwardly through conduit 8, but will be discharged through line 32.

Of course, the figures above givenl are not absolute values which must be used, but merely indicate relative values which may be advantageously employedpat different points in the system. With relative gas pressures of the order above mentioned, the required heightof the cat` alyst' column above the reactor and above the re generator is minimized with the result that the overall height of the structure can be kept at a minimum. The example above given neglects consideration of the stripping columns 3 and 1, but when these vessels are used it will be apparent that the gas pressures above given may be adjusted to compensate for the drop in pressure encountered by the stripping gas in passing through the strip-l ping zones. When stripping columns 3 and 1 ,are employed, as is usually desirable, I further contemplate making conduits 4 and 8 sulciently long and of suihciently smaller cross-section than the' stripping columns that the stripping gas would encounter more resistance in flowing downwardly with the catalyst through conduits 4 and 8 than in owing upwardly through the catalyst beds in the respective stripping columns. This mini mizes introduction of stripping gas from line 39 into-the reactorv and introduction of stripping gas from line 20 into the regenerator.l Conduit 6 is also of sui'icient length that stripping gas will be-discharged from the space above bed I9'v in column 1 through vline 24 rather than pass upwardly into the reactor through conduit'G.

Thecatalyst or contact material employed in the present process is preferably in the form of small substantially spherical particles. The size of' thesolid particles, Whether spherical or of other regular or irregular shape, is suiilcient that' they will rnot be excessively compacted to give ya high pressure drop for the fluids which are passed inv contact therewith when beds 'of substantial depth are employed in the reaction, vregenerating and stripping zones. However, their size or, more particularly, their average density is not suf nature shouldbe avoided so that these small particleswill not` excessively ll the voids between thelarger particles and give a high pressure drop for the reactants and regenerating gases passing through the beds.. For this reason, the particles c hargedpto the system are preferably of substan-- t1 yfuniform o r well graded sizeand anyexqefs'sive quantity of nes produced byattritionof. the larger particles' withinthe system isv preferably removed -from the vsystem and replaced by' larger particles. To avoid excessive attrition the particles should" have good structural strength, The use. of "substantially spherical particles willV also greatly assist in avoiding excessive attrition.

One suitable method of preparing spherical or substantially spherical synthetic catalysts of the type which may be advantageously used in the present process is disclosed in application Serial Number 516,392 of Glenn M. Webb and Reno W. Moehl, led December 31, 1942.

I claim:

1. A conversion process which comprises contacting hydrocarbons at conversion temperature with subdivided solid catalyst in a reaction zone, removing contaminated catalyst particles from said zone and burning contaminants therefrom in contact with oxygen-containing gas in a regenerating Zone maintained under pressure, separately removing resultant combustion gases and regenerated catalyst particles from the regenerating zone, suspending the withdrawn regenerated particles in at least a portion of said combustion gases, passing the resultant suspension through a cooling Zone, introducing the cooled suspension into a separating zone disposed at a higher elevation than said reaction Zone and maintained under lower pressure than the regenerating Zone, the pressure differential between said regenerating and separating Zones being such as to impart to said combustion gases sufficient kinetic energy to eiect said transportation of the regenerated catalyst particles from the regenerating Zone to the separatingzone,

separating catalyst particles from the combus-v tion gases in the last-named zone, supplying a portion of the cooled regenerated catalyst directly from said separating zone to the regenerating Zone without passage thereof through the reaction Zone, and passing another portion of the regenerated catalyst downwardly by gravity from the separating zone to the reaction Zone.

2. The process as defined in claim 1 further characterized in that the separating zone is dis- 10 posed at a higher elevation than the regenerating Zone and in that the regenerated catalyst particles are transported thereto by the gas-lift action of combustion gases from the regenerating zone.

3. The process as dened in claim 1 further characterized in that the reaction zone and the regenerating zone are disposed in vertical alignment and the catalyst passed downwardly therethrough in the form of an uninterrupted relatively dense column.

4. The process as defined in claim 1 further characterized in that the suspension of regenerated catalyst in combustion gases is cooled by indirect heat exchange with a cooling uid, whereby to recover heat from both the catalyst and the combustion gases.

5. A conversion process which comprises contacting hydrocarbons at conversion temperature with subdivided solid catalyst in a reaction zone, removing contaminated catalyst particles from said Zone and burning contaminants therefrom in contact with oxygen-containing gas in a regenerating zone, separately removing resultant combustion gases and regenerated catalyst particles from the regenerating zone, suspending the withdrawn regenerated particles in at least a portion of said combustion gases, passing the resultant suspension through a cooling zone, introducing the cooled suspension into a separating Zone disposed at a higher elevation than said reaction Zone, separating catalyst particles from the combustion gases in said separating zone, supplying a portion of the cooled regenerated catalyst directly from said separating Zone to the regenerating Zone without passage thereof through the reaction zone, and passing another portion of the regenerated catalyst by gravity from the separating zone to the reaction zone.

` QLARENCE G, GERHOLD? 

